INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2025
·
IF 3.9
Kangxin Bai,Yang Liu,Zhuangzhi Li,Jiajie Shi,Zhenggong Wang,Jian Jin
The separation of C2H4/C2H6 is crucial for the efficient production of C2H4. The energy-efficient membrane technology has great potential in this separation. However, the similar physical properties of the two molecules make them extremely difficult in membrane separation. Herein, a series of nanosized MOF-808 particles were incorporated into a polyimide matrix to fabricate mixed matrix membranes (MMMs) for C2H4/C2H6 separation. The well-defined pore architecture of MOF-808 enables effective C2H4 purification through molecular sieving, while the restricted diffusion of C2H6 molecules within the MOF-808 channels facilitates remarkable kinetic separation. Importantly, the nanosized MOF-808 can be dispersed more evenly in the polymer matrix, significantly improving the compatibility between the polymer matrix and filler, thereby maximizing the sieving effect of MOF-808. The resulting nanosized MOF-808-based MMM demonstrates a high C2H4 permeability of 1187 barrer and a C2H4/C2H6 selectivity of 2.8, which has exceeded most of the MMMs reported so far and surpassed the 2013 upper bound. Our MMMs also show excellent long-term stability and antiplasticization performance. Our work highlights the effectiveness of enhancing the separation performance of MMMs by using reducing nanosized MOF-808, providing valuable insights for the design of MMMs for C2H4/C2H6 separation.
研究领域:
膜技术
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气体分离
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材料科学
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化学工程
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纳米技术
✓ 已验证
产品关联
DOI
高影响因子
FUEL PROCESSING TECHNOLOGY
·
2023
·
IF 7.5
Weicong Xu,Peijun Li,Nan Wang,Xiaowen Ding,Yujia Chen,Beichen Xue,Tao Li,Chao Liu,Rui Xiao
Electrocatalytic reduction is a promising strategy for CO 2 utilization, while the conversion of CO 2 to C 2 products usually suffers from the low selectivity. Herein, we report several high-performance Cu-OCN catalysts for electroreduction CO 2 -to-C 2 H 4 , which are prepared through the in-situ calcination of nanocube Cu 2 O and urea. The highest C 2 H 4 faradaic efficiency from Cu-OCN-10 reaches 55.97%, much higher than that from the pristine CuO counterpart (38.31%), with a partial current density of −12.83 mA cm −2 . Catalyst characterizations and first-principles density functional theory calculations reveal that the superior performance of CuO-OCN is attributed to the introduced nitrogen (N) species and oxygen (O)-vacancies. With the assistance of N species and O-vacancies, the adsorption of CO 2 on Cu-OCN-10 is thermodynamically favorable with the absorption energy of −0.69 eV. Meanwhile, the activation of CO 2 is promoted and the generated *CO intermediate on Cu-OCN-10 is stable, whose release needs to overcome an energy of 2.26 eV, thereby enhancing the C C coupling to produce C 2 H 4 . In general, the synergistic effects of N species and O-vacancies in Cu-OCN catalysts facilitate CO 2 electroreduction to C 2 H 4 .
研究领域:
电化学
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催化
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材料科学
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环境科学
✓ 已验证
产品关联
DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2024
·
IF 20.2
Lili Huang,Shengpeng Mo,Xin Zhao,Jiangjing Zhou,Xiaobin Zhou,Yanan Zhang,Yinming Fan,Qinglin Xie,Bing Li,Junhua Li
Herein, a core-shell structured Co 3 S 4 /NC@ZnS/NC heterojunction has been constructed via elaborately synthesizing metal-organic framework (MOF)-on-MOF precursors (ZIF-67@ZIF-8) and following controlled carbonization-sulfidation processes. The developed Co 3 S 4 /NC@ZnS/NC achieves higher performances for CO 2 photoreduction with water vapor towards CO (28.44 μmol g −1 h −1 ), CH 4 (1.93 μmol g −1 h −1 ) and C 2 H 4 (12.23 μmol g −1 h −1 ) in a continuous-flow condition under visible-light irradiation, which are significantly superior than those of Co 3 S 4 /NC and ZnS/NC. 13 CO 2 isotope tracer analysis verifies that CO, CH 4 and C 2 H 4 originate from the carbon source of CO 2 . Experiments and DFT calculations confirm that constructing an electron transport layer (ZnS/NC) in Co 3 S 4 /NC@ZnS/NC can contribute to a feasible channel for the enhanced separation and transfer of charge carriers. In heterojunction , non-bonding Co and Zn atomic pairs as adsorption sites synergistically participate in the CO 2 activation through the unique electron transport channel and acquire the lower energy barriers of COOH* formation. Moreover, in situ DRIFTS reveals the key intermediates and possible conversion pathways to main products. This work presents an attractive strategy to construct dual MOFs-derived metal sulfide heterojunctions for high-performance CO 2 conversion.
研究领域:
材料科学
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环境科学
✓ 已验证
产品关联
DOI
高影响因子
INORGANIC CHEMISTRY
·
2024
·
IF 4.3
Jia-Nuo Li,Ding Chen,Yunli Wang,Jia Li,Yuqiao Chai,Xunwen Xiao,Xing Li,Jin-Peng Xue
Multi-interpenetrated metal–organic frameworks (MOFs) have exhibited excellent performance in selective adsorption due to the variable post-interspersed flexibility, but the design and control remain challenging. Herein, two anthracene-based ligands, 4,4′-(anthracene-9,10-diyl)dibenzoic acid (H2L1) and 9,10-di(pyridin-4-yl)anthracene (L2), are used to construct a new three-dimensional 6-fold interpenetrated MOF [Zn(L1)(L2)]n (NBU-X1), which exhibits multiple C–H···π interactions that enhance the structural rigidity, thereby entangling with a C2H2/C2H4 separation performance. In this material, the incorporation of abundant anthracene rings within the framework not only partitions and restricts the pore window size to a quasi-double pore but also stabilizes it through host–host interactions. The structural stability upon heating or guest displacement/removal has been investigated by single-crystal X-ray diffraction and in situ variable-temperature powder X-ray diffraction, in contrast to the extreme flexibility of most multi-interpenetrated MOFs. The performance of purifying C2H4 from C2H2/C2H4 mixtures has been proved by dynamic breakthrough tests.
研究领域:
材料科学
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化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2024
·
IF 20.2
Yu Nie,Yanfang Li,Chao An,Xin Tan,Zhuofeng Hu,Jinhua Ye,Tao Yu
Ethylene production by CO 2 reduction is sluggish because the repulsive dipole-dipole interaction and 12 proton-coupled electron-transfer steps consecutively. Amorphous structured photocatalysts possess few grain boundaries and abundant unsaturated sites, accelerating the reaction efficiency from the angle of dynamics and thermodynamics, which still not yet be used in PCR to C 2 products currently. Herein, an amorphous Cu x CoS y composed of the minority crystalline CuCo 2 S 4 is fabricated to realize an excellent C 2 H 4 selectivity in terms of R electron (94.9%). Unsaturated Co and S play the key roles in the improved efficiency of C 2 H 4 generation. C-C coupling is achieved via shortening Co-S bonds distance, and *CO-*CO coupling barrier is decreased by more electrons accumulated on unsaturated S. Water is adsorbed on Co adjacent to S and provide protons for *COCO to form *CH 2 = C. This work paves a new way for broadening the efficient of C 2 H 4 photocatalytic evolution using amorphous photocatalyst.
研究领域:
化学
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材料科学
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环境科学
✓ 已验证
产品关联
DOI
高影响因子
Nano-Micro Letters
·
2023
·Vol. 15
·期 1
·1-15
·
IF 26.6
Li Minhan,Zhang Fangzhou,Kuang Min,Ma Yuanyuan,Liao Ting,Sun Ziqi,Luo Wei,Jiang Wan,Yang Jianping
Electrochemical reduction of CO 2 into high-value hydrocarbons and alcohols by using Cu-based catalysts is a promising and attractive technology for CO 2 capture and utilization, resulting from their high catalytic activity and selectivity. The mobility and accessibility of active sites in Cu-based catalysts significantly hinder the development of efficient Cu-based catalysts for CO 2 electrochemical reduction reaction (CO 2 RR). Herein, a facile and effective strategy is developed to engineer accessible and structural stable Cu sites by incorporating single atomic Cu into the nitrogen cavities of the host graphitic carbon nitride (g-C 3 N 4 ) as the active sites for CO 2 -to-CH 4 conversion in CO 2 RR. By regulating the coordination and density of Cu sites in g-C 3 N 4 , an optimal catalyst corresponding to a one Cu atom in one nitrogen cavity reaches the highest CH 4 Faraday efficiency of 49.04% and produces the products with a high CH 4 /C 2 H 4 ratio over 9. This work provides the first experimental study on g-C 3 N 4 -supported single Cu atom catalyst for efficient CH 4 production from CO 2 RR and suggests a principle in designing highly stable and selective high-efficiency Cu-based catalysts for CO 2 RR by engineering Cu active sites in 2D materials with porous crystal structures.
研究领域:
化学
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材料科学
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电化学
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环境科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
ACS Nano
·
2023
·
IF 17.1
Yanfei Sun,Jiangzhou Xie,Zhenzhen Fu,Huiying Zhang,Yebo Yao,Yixiang Zhou,Xiaoxuan Wang,Shiyu Wang,Xueying Gao,Zheng Tang,Shuyuan Li,Xiaojun Wang,Kaiqi Nie,Zhiyu Yang,Yi-Ming Yan
Efficient conversion of carbon dioxide (CO2) into value-added materials and feedstocks, powered by renewable electricity, presents a promising strategy to reduce greenhouse gas emissions and close the anthropogenic carbon loop. Recently, there has been intense interest in Cu2O-based catalysts for the CO2 reduction reaction (CO2RR), owing to their capabilities in enhancing C–C coupling. However, the electrochemical instability of Cu+ in Cu2O leads to its inevitable reduction to Cu0, resulting in poor selectivity for C2+ products. Herein, we propose an unconventional and feasible strategy for stabilizing Cu+ through the construction of a Ce4+ 4f–O 2p–Cu+ 3d network structure in Ce-Cu2O. Experimental results and theoretical calculations confirm that the unconventional orbital hybridization near Ef based on the high-order Ce4+ 4f and 2p can more effectively inhibit the leaching of lattice oxygen, thereby stabilizing Cu+ in Ce-Cu2O, compared with traditional d–p hybridization. Compared to pure Cu2O, the Ce-Cu2O catalyst increased the ratio of C2H4/CO by 1.69-fold during the CO2RR at −1.3 V. Furthermore, in situ and ex situ spectroscopic techniques were utilized to track the oxidation valency of copper under CO2RR conditions with time resolution, identifying the well-maintained Cu+ species in the Ce-Cu2O catalyst. This work not only presents an avenue to CO2RR catalyst design involving the high-order 4f and 2p orbital hybridization but also provides deep insights into the metal-oxidation-state-dependent selectivity of catalysts.
研究领域:
电化学
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材料科学
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催化
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可再生能源
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环境科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Chemical Science
·
2024
·Vol. 15
·期 24
·9173-9182
·
IF 7.6
Jiye Feng,Wenbiao Zhang,Danni Shi,Yingshuai Jia,Yi Tang,Yuying Meng,Qingsheng Gao
Multi-phase interfaces are promising for surmounting the energy barriers of electrochemical CO2 reduction involving multiple electron transfer steps, but challenges still remain in constructing interfacial micro-structures and unraveling their dynamic changes and working mechanism. Herein, highly active Ag/Cu/Cu2O heterostructures are in situ electrochemically restructured from Ag-incorporating HKUST-1, a Cu-based metal–organic framework (MOF), and accomplish efficient CO2-to-C2H4 conversion with a high faradaic efficiency (57.2% at −1.3 V vs. RHE) and satisfactory stability in flow cells, performing among the best of recently reported MOFs and their derivatives. The combination of in/ex situ characterizations and theoretical calculations reveals that Ag plays a crucial role in stabilizing Cu(I) and increasing the CO surface coverage, while the active Cu/Cu2O interfaces significantly reduce the energy barrier of C–C coupling toward the boosted ethylene production. This work not only proves MOFs as feasible precursors to derive efficient electrocatalysts on site, but also provides in-depth understanding on the working interfaces at an atomic level.
研究领域:
材料科学
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电化学
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催化
·
能量转换
✓ 已验证
产品关联
DOI
PubMed
高影响因子
CHINESE JOURNAL OF CHEMICAL ENGINEERING
·
2021
·
IF 3.171
Xionghui Liu,Jianfeng Du,Yu Ye,Yuchuan Liu,Shun Wang,Xianyu Meng,Xiaowei Song,Zhiqiang Liang,Wenfu Yan
Nitrogen-rich porous organic polymers have shown great potentials in gas adsorption/separation, photocatalysis , electrochemistry, sensing and so on. Herein, 1,2,3-triazole functionalized triazine-based porous organic polymers (TT-POPs) have been synthesized by the copper-catalyzed azide-alkyne cycloaddition (Cu-AAC) polymerization reactions of 1,3,5-tris(4-azidophenyl)-triazine with 1,4-diacetylene benzene and 1,3,5-triacetylenebenzene, respectively. The characterizations of N 2 adsorption at 77 K show TT-POPs possess permanent porosity with BET surface areas of 666 m 2 ·g −1 (TT-POP-1) and 406 m 2 ·g −1 (TT-POP-2). The adsorption capacities of TT-POPs for CO 2 , CH 4 , C 2 H 2 and C 2 H 4 , as well as the selective separation abilities of CO 2 /N 2 , CO 2 /CH 4 , C 2 H 2 /CH 4 and C 2 H 4 /CH 4 were evaluated. The gas selective separation ratio of TT-POPs was calculated by the ideal adsorbed solution theory (IAST) method, wherein the selective separation ratios of C 2 H 2 /CH 4 and C 2 H 4 /CH 4 of TT-POP-2 was 48.4 and 13.6 (298 K, 0.1 MPa), which is comparable to other adsorbents (5.6–120.6 for C 2 H 2 /CH 4 , 10–26 for C 2 H 4 /CH 4 ). This work shows that the 1,2,3-triazole functionalized triazine-based porous organic polymer has a good application prospect in natural gas purification.
研究领域:
材料科学
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化学工程
·
环境科学
✓ 已验证
DOI
高影响因子
MICROPOROUS AND MESOPOROUS MATERIALS
·
2025
·
IF 4.7
Jilong Peng,Xunqian Zhang,Rongqing Qin,Fang Lai,Na Shi,Qinggang Ren,Kungang Chai
In the petrochemical industry, efficiently achieving one-step purification of ethylene (C 2 H 4 ) from propylene (C 3 H 6 ) or ethane (C 2 H 6 ) is a highly sought-after yet challenging task. Herein, we present a chlorine-rich Zn-based metal-organic framework (DMOF-1-Cl 2 ) that retains the essential topology of the parent DMOF-1 through the incorporation of 2,5-dichloroterephthalate linkers. The chlorine atoms within the square pores of DMOF-1-Cl 2 , due to their high electronegativity, serve as potential adsorption sites. Gas adsorptive experiments revealed its preferential adsorption of C 3 H 6 and C 2 H 6 over C 2 H 4 at different temperatures. Ideal adsorption solution theory calculation revealed that the selectivity of DMOF-1-Cl 2 for C 3 H 6 /C 2 H 4 and C 2 H 6 /C 2 H 4 reaches 20.8 and 2.2 at 313 K, respectively, outperforming its counterpart (DMOF-1-Br 2 ) and most previously reported adsorbents. Theoretical calculations indicated that the gas molecules are primarily distributed around the chlorine atoms with multiple interactions. Furthermore, dynamic breakthrough experiments fully demonstrated the actual potential for achieving one-step purification of polymer-grade C 2 H 4 , in which DMOF-1-Cl 2 displayed high productivity of 206.1 and 31.6 L kg −1 from C 3 H 6 /C 2 H 4 (2/5, v/v) and C 2 H 6 /C 2 H 4 (1/9, v/v), respectively. Despite the fact that the yield of C 2 H 4 separation from C 2 H 6 /C 2 H 4 mixtures is not extremely high, it still remains at a satisfactory level, demonstrating the practical value and potential of DMOF-1-Cl 2 for industrial applications.
研究领域:
材料科学
·
化学工程
✓ 已验证
产品关联
DOI
高影响因子
VACUUM
·
2024
·
IF 3.8
Xiu Wen,Zhixiu Yang,Lijing Gao,Ruiping Wei,Xiaomei Pan,Jin Zhang,Guomin Xiao
Electrocatalytic reduction of CO 2 affords a potential way to mitigate the greenhouse effect and fuel crisis. In this work, we compared highly-dispersed CuO nanocomposites and Cu–Cu 2 O nanocomposites which all derived from Cu x Al-LDH for CO 2 electrochemical reduction . The Cu–Cu 2 O based nanocomposites obtained through the restoration strategies still retain its layered structure, simultaneously increasing dual Cu–Cu 2 O active sites, which exhibit excellent performance in selective reduction of CO 2 to C 2 H 4 . The Cu 5 Al-ER obtained through in-situ electrochemical reduction is modified by bulk phase, which can regulate active species, increase surface active sites, enhance C–C coupling. Meanwhile, the electrochemical strategy offers numerous benefits, including gentle conditions, adjustable monitoring, exceptional efficiency and adaptability. We have confirmed that cost-effective Cu–Cu 2 O based nanocomposite derived from Cu 5 Al-LDH can effectively promote C–C coupling during electrochemical CO 2 conversion and improve FE C2H4 . The FE C2H4 of Cu 5 Al-ER reaches 36% at −1.2 V vs. RHE. And the current density reaches −172 mA·cm −2 at −1.6 V vs. RHE. The results showed that compared to Cu 5 Al-LDO, the FE C2H4 of Cu 5 Al-ER increased by 2.6 times. In addition, Cu 5 Al-ER exhibits excellent stability during the 12 hours CO 2 catalytic reduction process.
研究领域:
化学
·
环境科学
·
能源科学
✓ 已验证
产品关联
DOI
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
·
2023
·
IF 8.6
Ye Li,Yong Wang,Honghao Bai,Shishuai Li,Xiaomin Li,Xiaoqing Wang,Libo Li,Jinping Li,Jiangfeng Yang
The economically efficient separation of ethane (C 2 H 6 )/ethylene (C 2 H 4 ) presents challenges in the petrochemical industry, and the use of traditional adsorbents zeolite provides a reliable guarantee for maintaining the economic viability of adsorption separation technology. In this study, we investigate the impact of different silica-alumina ratios (SiO 2 /Al 2 O 3 = 40, 500, and 1500) of high silica zeolites ZSM-11 on the C 2 H 6 /C 2 H 4 separation performance to develop efficient C 2 H 6 selective adsorbents. The results show that the C 2 H 6 adsorption capacity and C 2 H 6 /C 2 H 4 selectivity of ZSM-11 increase as the silica-alumina ratios increases. The pure silica zeolite (ZSM-11(1500)) exhibits the highest adsorption capacity for C 2 H 6 (59.19 cm 3 /g) and the highest selectivity for C 2 H 6 /C 2 H 4 (2.04), which were superior to ultra-high silica sample (ZSM-11(500)) (55.06 cm 3 /g and 1.62, respectively) and high silica sample (ZSM-11(40)) (47.28 cm 3 /g and 1.23, respectively), at 273 K and 1 bar. The mixed gas breakthrough experiments results show that pure silica sample has outstanding C 2 H 6 /C 2 H 4 separation ability. The PSA simulation calculated data demonstrating promising potential for industrial applications. Importantly, this separation performance remains unaffected even in the presence of H 2 O.
研究领域:
化学工程
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）